5.

Solutions of Schrödinger equation for simple systems

5.1 Introduction
 To find the properties of systems according to quantum
mechanics, we need to solve the appropriate Schrödinger
equation.
 The essentials of the solutions for three basic types of
motion: translation, vibration, and rotation are considered.
Outcome:
 Only certain wavefunctions and their corresponding energies
are acceptable.
 Quantization emerges as a natural consequence of the
equation and the conditions imposed on it.
1
5.2. Particle in box
5.2.1 Free particle in one dimensional box

 Imagine that a particle of mass m is free to move along the x-axis

between x = 0 and x = a.

 For the free particle,

 V = 0 for 0 < x < a.
 At x = 0 and at x = a, and at all points beyond these limits, the
particle encounters an infinitely repulsive barrier
The restrictive conditions are called boundary conditions.

2
 Particle in One Dimensional Box

Boundary conditions

Figure 1. The potential felt by a particle as a function of its x –

coordinate.

3
 Particle in One Dimensional Box

We have three regions to consider.

 In regions I and III (outside the box), the potential energy, V,
equals infinity.
 The time-independent Schrödinger Equation becomes:

 The equation is satisfied only if ψ is zero at all points outside the

box.

 If ψ is zero, ψ2= 0 and hence the probability of finding the

particle outside the box is negligible.

4
 Particle in One Dimensional Box

 In region II (inside the box), the potential energy, V, is zero and the
Schrödinger Equation becomes

Let

The above equation becomes

Real solution

5
 Particle in One Dimensional Box

Because of the boundary condition, at x = 0, ψ(0) = 0.

Accordingly,

Therefore, the constant C is equal to zero.

 The equation reduces to
 (x) = 𝐷 𝑠𝑖𝑛𝑘𝑥
At x = a,  (a) = 0
 (a) = 𝐷 𝑠𝑖𝑛𝑘𝑎 = 0
 The constant D has to be different from zero.
 Otherwise the wave equation will be zero everywhere.
 Therefore sin ka has to be equal to zero.
 This is possible only if ka is a multiple of nπ where n is an integer.
6
 Particle in One Dimensional Box

 Since ψ(n) = ψ(-n), only the positive values of n are considered.

Therefore,

Substitution yields

 If n = 0, k becomes zero and the equation will always be zero

 unacceptable condition.
 k has to be different from zero  n has to be different from zero.
7
 Particle in One Dimensional Box

Acceptable solution of the time-independent Schrödinger equation

for a free particle in a box is

n is called a quantum number.

 The allowed values of n are the positive integers.
From the above relations;

Equating the two together yields,

8
 Particle in One Dimensional Box

 The boundary condition forces to the conclusion that the values

of the energy are quantized

 The particle in the box can have only certain restricted values of
energy.
 This is in contrast to the classical result that the particle can have
any non-negative energy.
 The energy difference between two consecutive levels increases
as the value of n increases.

9
 Particle in One Dimensional Box

 Note: Because of the extremely small magnitude of Planck’s

constant, quantization of energy is unobservable for macroscopic
bodies.

Ground state: The state of lowest energy.

The lowest energy ( n = 1) is called the zero point energy.
ℎ2
𝐸1 =
8𝑚𝑎2
Excited states: States with energies higher than the ground-state
energy.

10
 Particle in One Dimensional Box

Figure 2. The lowest four energy levels for the particle in a one-dimensional
box.

The separation between adjacent energy levels with quantum

numbers n and n + 1 is:
𝑛 + 1 2ℎ2 𝑛2ℎ2 ℎ2
𝐸 n+1 − 𝐸 n = 2
− 2
= 2𝑛 + 1
8𝑚𝑎 8𝑚𝑎 8𝑚𝑎2 11
 Particle in One Dimensional Box

Example:
A particle of mass 2.0 × 10-26 g is in a one-dimensional box of length 3
nm. Find the frequency of the photon emitted when the particle
goes from n = 2 to n = 1 state.
Solution
The energy difference between two consecutive energy levels is
given by: ∆𝐸 = ℎ

12
 Particle in One Dimensional Box

Determination of the coefficient, D

 D can be determined by making use of the normalization
condition.

The normalized wave function for a particle in one-dimensional box

13
 Particle in One Dimensional Box

Figure 3. Graphs of a) ψ and b)|ψ|2 for the three lowest-energy particle in a box
states.
14
 Particle in One Dimensional Box

 For n ≠ 1, the wave function is zero at certain points, called

nodes.
 For each increase of one in the value of n, there is one more
node.
 Classically, a particle of fixed energy in a box moves at
constant speed and is equally likely to be found at any point
in the box.
 Quantum mechanically, we find maximum/s in probability at
certain locations depending on the energy level.

15
 Particle in One Dimensional Box

Example:
Calculate the probability that a particle in a one-dimensional box of
𝑎
length a is found to be between 0 and
2
Solution

 For higher quantum numbers, we approach the classical result of

uniform probability density.

16
 Particle in One Dimensional Box

Example
Calculate the average momentum, P , of a particle in a box.
Solution:

 1
  1

a
 
2 n x   i h d   2 n x
 p     sin  dx  0
2 2

 a     sin
0 
a   2 dx   a  a 
   

 Thus, a particle in a box is equally likely to be moving in either

direction.
17
5.2.2. Free Particle in a three - dimensional box

Where 2 is the Laplacian operator

 As before, the particle has no probability for penetrating beyond

the box and as a result ψ vanishes at the box edges.

18
 Particle in Three - Dimensional Box

 Use the method of separation of variables to solve the equation

 (x, y, z).

Solution

19
 Particle in Three - Dimensional Box

Normalized wave function

20
 Particle in Three - Dimensional Box

For a cubic box; a = b = c

The lowest energy level (E111) is non-degenerate.

The second energy level is three-fold degenerate, i.e.,

21
5.2.3. Free Electron Model for Conjugated Hydrocarbons

 The model of a particle in a one-dimensional box has been

applied to the  electrons in linear conjugated
hydrocarbons.

 Consider butadiene, H2C=CHCH=CH2, which has four 

electrons
 The  electrons are assumed to move along a straight line
whose length can be estimated to be 578 pm.
 Electron arrangement: two electrons in n = 1 state and two
electrons in n = 2 state.
22
 Free Electron Model for Conjugated Hydrocarbons

 In the first excited state, one electron will be elevated from

n = 2 state to n = 3.
 The energy needed to make the transition is:

 6.626 10 Js 
34 2
2
E 
h
 32
 2 2
   5  9.02  10 19
J
8  9.109 10 kg   578 10 m 
2   2
8me a 31 12

 This corresponds to   4.54 104 cm1

 Experimentally, butadiene has an absorption band at 4.61 ×
104 cm-1.
 Therefore, the model explains the absorption spectrum of
butadiene.
23
 Free Electron Model for Conjugated Hydrocarbons

5.2.4. Particle in a Rectangular Well

 Consider a particle in a one-dimensional box with walls of

finite height.

Vo for x < 0 and x > l

Vo Vo
V=
I II III 0 for 0  x  l

0 l

 For the particle in a rectangular well there is a non-zero

probability of finding the particle in regions I and III, where its
total energy is less than its potential energy.
24
 Particle in a Rectangular Well

  oscillates inside the box and dies off exponentially outside

the box.

Example: For the ground state;

 Classically, this behavior is not allowed.

 According to the classical equations; E = T + V and T  0
 E cannot be less than V.
 The particle cannot escape from the box unless its energy is
greater than the potential-energy barrier, Vo.
25
 Particle in a Rectangular Well

 According to quantum mechanics, there is a finite probability for a

particle of E < Vo to be found outside the box.

Tunneling
 The penetration of a particle into a classically forbidden region
or
 The passage of a particle through a potential energy barrier
whose height exceeds the particle’s energy.
 Tunneling is a quantum effect.
 Therefore, it is most prevalent with particles of small mass.
 Electrons tunnel quite readily.
 Hydrogen atoms and ions tunnel more readily than heavier
atoms.
26
5.3. Harmonic Oscillator
 It is a system with a continuously varying potential.
 Quantum mechanical harmonic oscillator plays an essential
role in our understanding of molecular vibrations, their spectra
and their influence on thermodynamic properties.

5.3.1. Classical Treatment of One-Dimensional Harmonic

Oscillator
 Approximation: A pendulum consisting of a large mass hanging
by an almost weightless wire, and swinging through a very
small angle

27
 Harmonic Oscillator

 Oscillator  its motion is back and forth over the same path.
 Harmonic  the restoring force on the mass is proportional to the
horizontal component of the displacement of the mass.

𝑑2𝑥 𝑑 2𝑥 𝑘
𝐹 = −𝑘𝑥 = 𝑚𝑎 = 𝑚 2 + 𝑥 =0
𝑑𝑡 𝑑𝑡2 𝑚
Solution

𝑘
𝑥 = 𝐴𝑐𝑜𝑠 𝑡
𝑚

𝑥 = 𝐴𝑐𝑜𝑠𝑡
where
𝑘
=
𝑚
28
 Harmonic Oscillator

Fig. An illustration of the displacement of a harmonic oscillator

versus time.

x repeats itself whenever the cosine increases by 2.

This will require a certain time interval t.

𝑘 𝑚
𝑡 = 2𝜋 𝑡 = 2𝜋
𝑚 𝑘
29
 Harmonic Oscillator

 Therefore, the frequency of the oscillator  is

1 1 k 
  
t 2 m 2

k  4 m
2 2

30
5.3.2 The Quantum Mechanical Treatment of Harmonic Oscillator
 Force can be expressed as a derivative of a potential energy.
𝑑𝑉
𝑓 𝑥 =−
𝑑𝑥

 The potential energy is therefore,

1
𝑉 𝑥 = − 𝑓 𝑥 𝑑𝑥 = − −𝑘𝑥𝑑𝑥 = 𝑘𝑥2
2

 The one-dimensional Schrödinger equation for the harmonic

oscillator is therefore,
 h 2  d 2  1 2 
 2  2   kx  ( x )  E ( x )
 8 m  dx  2 
31
 Harmonic Oscillator

Substitute for k
 h2  d 2  
 2  2   2  mx  ( x )  E ( x )
2 2 2

 8 m  dx  

Further rearrangement gives

d 2 ( x ) 8 2 mE 16 4 2 m2 x 2
(  ) ( x )  0
dx 2 h 2
h 2
Let
4 2 m

h
d 2 ( x ) 8 2 mE
(   x ) ( x )  0
2 2

dx 2 h 2
32
 Harmonic Oscillator

Solution
 x2

 e 2
f( x)

where

f( x )   Cn x n

n 0
And
 + 2𝑛 − 2𝑚𝐸ħ−2
𝐶n+2 = 𝐶n
𝑛+1 𝑛+2

33
 Harmonic Oscillator

 Boundary condition:  = 0 at x =  ∞.
 Therefore the coefficient of Cn should be zero for some values
of n, say for n = .
Accordingly,
  2 n  2mE 2
0
Substituting the value of  give
1
E  (  ) h , where   0,1, 2,...
2
Using the expression for E,
2 ( n   ) Recursion relation
Cn  2  Cn
( n  1)( n  2)

where n + 2 = , for  different from 0 and 1

34
 Harmonic Oscillator

 If we know Co, we could produce C2, C4, C6, etc. Similarly,

knowledge of C1 would lead to C3, C5, etc.
 The coefficients for even and odd powers of x form separate
sets.
 x2
e 2 (Co  C x2  C x4  ...) for   even
   x2
2 4

e 2 (C x  C x3 C x5 ...) for   odd

1 3 5
Examples
Determine the normalized solution for the harmonic oscillation
wave function,
a. o b. 1 c. 2
35
 Harmonic Oscillator

Solution
In o,  = 0, and therefore the coefficient is Co. Therefore,
 x2

 o  Co e 2

Using normalization property,

1
  4
C0   
 
The normalized solution then becomes
1  x2
  4 
o    e 2

 

36
 Harmonic Oscillator

In 1,  =1, and therefore the coefficient is C1.

 x2

 1  C1 xe 2

Normalized solution
 x2
 4  
3
1   e
2

  

c. In 2,  = 2. using the recursion relation,

Cn + 2 = C2. Therefore, n = 0.
Accordingly,
2 (0  2)
C2  Co   2 Co
(0  1)(0  2)
37
 Harmonic Oscillator

Substitution yields,
 x2  x2  x2
  
 2  (Co  C2 x )e
2 2
 (Co  2 Co x )e2 2
 Co (1  2 x )e
2 2

Normalized solution
1
 x2
  4 
 2    (2 x 2  1)e 2

 
Exercise
Determine the normalized solution for the harmonic oscillation
wave function, 3.

38
 Harmonic Oscillator

Energy of a harmonic oscillator:

1
E  (  ) h , where   0,1, 2,...
2

 1 1 k
E  h    , where  0,1, 2,...
 2  2 m
The separation between adjacent levels is:
1 1 𝑘
𝐸+1 − 𝐸 = ℎ = ℎ  = ħ = ℎ
2𝜋 2𝜋 𝑚
ℎ
Where, ħ =
2𝜋

39
 Harmonic Oscillator

Fig. The parabolic potential energy and some allowed

energies of a harmonic oscillator

40
 Harmonic Oscillator

Important features of the harmonic oscillator

 The energy level spacing between two consecutive energy levels
is constant.
E = h
1
 It has a finite zero-point energy of ℎ for  = 0
2
 The particle has a finite probability of being found beyond the
classical turning points
Reason: The barrier is not infinite
 In the lowest-energy state, there is high probability of the particle
being in the low-potential central region of the potential well.
At higher energies there is high probability in the higher potential
regions.
41
 Harmonic Oscillator

5.3.3. Vibration of Diatomic Molecules

 The simple harmonic oscillator is a good model where two masses
are connected by a spring.
 The two masses are represented by a reduced mass, .
 The Schrödinger equation
h 2 d 2 1 2
  kx   E
2 dx 2
2
 Permitted energy levels
1 𝑘
𝐸 =  + ħ  = 0,1,2, … where,  =
2 
 In terms of wavenumbers
1
 1 1  k  2
      
 2  2 c   
42
 Harmonic Oscillator

Example: An HCl molecule has a force constant of 516 Nm-1. Its

reduced mass is 1.63×10-27kg. Calculate , , and E0.
Solution:
1 1 1
 k  2  516 Nm1  2  516 kg ms 2m1  2
        5.63 1014 s 1
  1.63 1027 kg   1.63 1027 kg 
   

 5.63 1014 s 1
   8.96 1013 s 1
2 2  3.14


8.96 1013 s 1
   2987 cm 1

c 3 1010 cms 1
 1 6.63 1034 Js
 5.63 1014 s 1  2.97 1020 J
h
E   0   h   
0  2 4 4  3.14
43
5.4. Rotational Motion

The Rigid Rotator

 A model for a rotating diatomic molecule consists of two point
masses m at fixed distances from their center of mass – the
reduced mass, .

 Consider a particle in a rotational motion under the influence

of time-independent potential.
 The potential is either constant or position–dependent.
 The rotational motion is described in terms of the polar
coordinates.

44
 The Rigid Rotator

z  r cos
x  r sin cos
y  r sin sin 

 The Laplacian operator, 2, in the spherical polar coordinates

then becomes

1     1     1  2
2  2  r 2   2  sin  2 2
r r  r  r sin     r sin   2
45
5.4.1 Particle on a ring
Let radius = constant = R,  = /2, V = 0
1  2
2  2
R  2
The time independent Schrödinger equation reduces to

2 8 2 mER 2
  0
 2
h 2

Let 8 2
mR 2
E
k2 
h2
Normalized solution:
1 in
 ( )  e , n  0,  1,  2,....
2
46
 Particle on a ring

Expression for the energy of a particle on a ring

h2k 2
E 2 2
8 mR
2 2
h n
With k = n, E  2 2 , n  0,  1,  2, ...
8 mR
 All the energy levels are doubly degenerate except the ground
state where E0 = 0.

Ground state wave function:

1
 0 ( ) 
2
 The particle is uniformly distributed in the given space and that
its position is completely uncertain
47
5.4.2 Particle on a sphere

Let V = 0, radius = R = constant

8 2
E

2
2
 0
h
 1    1 2   8 2 E
  sin   2 
2   ,  
   ,   0
I  sin     sin     h 2

 1    1 2   8 2 IE
  sin   2 
2   ,  
   ,   0
 sin    sin    2
 h

Where, I = R2 = moment of inertia

48
 Particle on a sphere

Letting

 ( , )  ( ) ( )
and multiplying by
sin 2
 yields
 ( ) ( )
sin     8 IE
2
1  2
 sin  ( )      ( )
2
sin
 ( )     h 2
 ( )  2

Let each side of the equation be equal to a constant, m2.

49
 Particle on a sphere

The  Equation

2
 ( )  m 2
 ( )  0
 2

Solution:
1 im
 m ( )  e where m  0,  1,  2, ...
2
The  Equation

sin     8 IE
2
 sin  ( )    
2 2
sin m
 ( )     h2

50
 Particle on a sphere

Let
8 2 IE
 2
h

sin     
 sin   ( )    sin 2
  m 2
0
 ( )    

If  = 𝑙 𝑙 + 1

Normalized solution of the  equation

1
 (2l  1) (l  m )! m
2
 l , m ( )    Pl (cos  )
 2 (l  m )! 
51
 Particle on a sphere

where

l m
l  0,1, 2,...
m   l ,  l  1, ...0, ...l  1, l
m m
d
Pl (cos )  (1  cos2  ) Pl (cos )
m 2

d cos 
m

1 d l (cos2   1) l
Pl (cos )  l
2 l! d cosl 

52
 Particle on a sphere

Solution of the Schrödinger Equation for a Particle on a Sphere

 l , m( ,  )   l , m( ) m( )  Yl , m( ,  )

1
  2l  1  l  m  ! m
2
Yl , m ( , )    l
P (cos  ) e  im

 4  l  m  !

m   l ,  l  1, ...0, ...l  1, l

 For a given value of l there are 2l + 1 values of m.

Expression for the energy of the particle on the sphere
h2
El  l (l  1), l  0,1, 2,...
8 I
2
53
 Particle on a sphere

For transition from l to l + 1 energy state

E  El 1  El
h2
 (l  1)(l  2)  l (l  1)
8 I2

h2
 2 (l  1), l  0,1, 2,...
8 I
 The values of l are quantized.
 the rotational kinetic energy of a particle on a sphere is
quantized.
 The energy does not depend on the quantum number, m.
 For a given value of l, there are 2l + 1 degenerate rotational
states.
54
 Particle on a sphere

L2 8 2 IE
Ek   2   l (l  1)
2I h
L2 h2
 2 l (l  1)
2 I 8 I
h
L l (l  1) l  0,1, 2, ...
2

 The angular momentum of a particle on a sphere is quantized.

55
 Particle on a sphere

Example: Write the lowest state wave function for a particle on a

sphere.
Solution
For the ground state, l = 0, m = 0

 2  0  1 0  0 ! 0
1 1
2
i 0 1 0 2
 0, 0( ,  )   0   P0 (cos )  1
0  0 !
P (cos ) e  
 4  4 
0 0
d
P0 (cos )  (1  cos2  ) 2 P0 (cos )  1  P0 (cos )
0

d cos 
0

1 d 0 (cos2   1) 0
P0 (cos )  0 1
2 0! d cos  0

1
1  2
 0, 0( , )   
 4  56